Vat dyestuff derivatives



Patented Jan. 24, 1933 (UNITED STA PATENT orl-" cs' JAMES MORTON, JAMES IvonMonGAn 'zronns, Ann IBIRKETT WIL'AM, on LANCASTER, AND JOHN EDMUND GUY HARRIS, or CARLISLEQENGLAND, ASSIGNORS T0. sco'r'rrsn nyns, LIMITED, or GRANGEMOUTH, SCOTLAND a q new process may be mentioned I VAT DYESTUFF DERIVATIVES No Drawing. Application filed August 10, 1925, SeriaLNo. 49,454, and in Great Britain August 11; 1 924. i

This invention relates to the art of dyeing and the production of vat dyestufl derivatives and materials dyed with the same and has for its main object to provide improvements in dyes and dyeing and more particularly themanufacture and use in dyeing and printing of stable and soluble derivatives of the herein after-described vat dyestuffs. These derivatives are intended to be used for direct dyeing and printing of animal and vegetable fabrics.

Among the dyestuffs to be treated by the Indigoid vat dyestuffs including indigo v and dichlor-dibrom-indigo;

Anthraquinone vat dyestuffs including benzanthrone, indanthrone, fiavanthrone, pyranthrone and anthraquinone acridone dyestuifs.

The invention consists in a process for the preparation of a dyeing compound according to which the dry. dyestufl' together with a suitable metallic powder is suspended in an organic tertiarybase and refluxed for a suitable time after which the resulting mixture is cooled and treated Withanalkyl sulphuric acid chloride.

The invention also consists in a process for the preparation of a dyeing compound according to which'the dry dyestuii, together with zinc powder, is suspended in pyridine, then refluxed, and cooled and treated with methyl sulphuric acid chloride, the dyeing compound being extracted from the resultant mass by the addition of a limited quantity of water and subsequent filtration;

The invention also consists in a dyeing process according to whichthe solid product resulting from the above process is dissolved in a suitable solvent and the articles to be dyed immersed in the solution, then treated-in a Example 1 This deals with Caledon jade green, zinc dust, pyridine, methyl sulphuric acid chloride and prior heating. i 3

In carrying the invention intoefi'ect in. one form by way of example, all ;parts in this specification being parts by weight, 2 parts of pure dry Caledon jade green (dimethoxydlbenzanthrone) are suspended q in 30 parts of pure pyridine and 6 parts .of zinc dust added. The mixture is then boiled und r a refluxcondenser for about10'minutes. The mixture is then allowed to cool and to, it is. added drop by drop from a tap funnel 10 parts of pure methylsulphuric acid chloride; A large amount of heat is evolved during this addition which may be spread over 10 to 15 minutes. The .mixture isgentlyagitated while the ester is added. The reddi'sh-brown paste resulting is poured into about 500 parts 1 of water, whereby abright red solution is.

formed and a quantity of dark red solid preg cipitated; The solution consists of a saturated solution of the reddish-brown solid and contains the bulk of the pyridine, which is I removedby filtration. ,The reddish-brown solid may be dissolved inhot water or alkali, and the resulting solution used for dyeing cotton, wool, naturalandartificial' silk. "The I parent dyestufi' may be regenerated on the fabric by treatment with mild acid oxidizing agents, such as acid ferric chloride solution.

Example 2 This deals with Caledon red BN, zinc, ya dine, and methyl sulphuric acid chloride on the lines of Example 1.

Anthraquinone acridone vat dyestuffs may i be treated on the lines of Examplel. In-the case of Caledon red BN," (anthraquinone- 1:2-naphthacridone) an orangesolid is obtained.

. Ezra/11237163- This deals with Caledon blue R and other chloride on the lines of Ex- I V thraquinone-azine) a dark red-violet com- Flavanthrone vat dyestufli's may be treatedonLtheli'nes-of Example 1. In the case-of Caledon yellowGr (flavanthrone) a dark blue,

solid is obtained, which is soluble in weak caustic soda solution to a blue-violetsolution and dyes cotton or other fibres blue-violet shades; which withsac'id oxidizing agentmay be developed to thoseof the original dyestufi'.

' r I EmampZ 5 v i This deals with Brilliant indigo BASF 2B and other= indigoid vat dyestufl's with zinc,

' pyridine and methyl sulphuric acid chloride on the lines of "Example-1.

Indigoid vat 'dyestuffs* may Brilliant indigo BASFQBhME: 4";dich1or- 7'ri'7l'ldi'brom'indig9l greenish-White solid Yum salt and methyl alcoholonsaponificationx is obtained. 5 v p I I Q Erample 6;

The crude products may be extracted with a -dilute alkali followed by; the salting out of a stable-product, which contains sufli'cientof the fiee-alkali-asa rule toensure the keeping propertie's'of the dyestuffs, the products be-- in'ggenerally speaking" most stable 1n 'the presence of a; little free'alkali. 1

I General invention is not limited tothe use of zinc dustcor methyl sulphuric acid chloride.

Any suitable metallic dustisuch' as copper, especially copper-bronze, for instance, may be used and any; other alkyl sulphuric acid chloride such asethyl sulphuric acid chloride may be usedp The organic base may be any suitable substance besidesrpyridine, for instance quinoline or'ydimethyl-aniline or a homologue or. substitution product ofthis type of b aseh- Among "the substances which may be dyed efi ectively-by the above process.

- may be noted cotton, wool, natural and artifi'cialsilkand straw.

Thef dyeing compounds produced by the abovesdescribed' process are in general stable to air, solubleinwater-and dilute alkali and in some cases are also soluble in dilute acids. They may be used-for'printing and for the direct dyeing of fabrics.

YAsa'n example of'a m'ethod'ofprinting,

3' parts of th e dry' dyestufi, derivative are made to a'thin paste with 2"'("parts o1 a 5% caustic soda solution- (or equivalent parts of adyestufl'j'fpaste may be used "with a? stronger so'da solution) and' 'the'n well mixed with be treated on' Atoms sulphur 'permoleoul-e of indigo; the-lines-of the dibenzanthrone dyestuff of Example 1' or Example 3. In the case of parts of a thickening containing 1 part of British gum to 1 part of water. The re- 7 sulting paste-is printed on textile materials in the usual manner, dried, steamed in a 'Mather & Plat-t or other steamer and treated with a bathi'of-"acid ferric chlorider In'connection with products which'can be prepared by processes herein described, th

following. information, is given,

Indigo 'b'odie's.The solubilityin cold ater maybe aboutr0.08 grammeslper lOO; cos. of water. The analysis of the purified and crystallized product may be as follows Per cent Apparently the indigobody'is not a sodium i-salt neither isit an alkyl ester 'ofzindi'go sulphuric-acid since-this-would yield a sodi- It appears to be in the. nature-of a quaternary alkyl pyridiniumderivative- :when':pre;-. Apparently-it-hasithe pared with pyridine. formula V to obtain' the disodium salt treatment with sodium hydroxide-or the like is effected] The resulting productis then easily soluble, Theprimary product when' pyridine has been employed appears to beacomplex containingthe pyridinium radicle' which breaks: down ontreatment with alkali.- In the decomposition of the primary product the pyridinium radicle is removed as a substance having a ch'aracteristicodour. The yellow f body on treatment with mineral acid is; converted into a blue-green variety, which'on treatment with alkali, turns purple, and in this treatment the red form loses halfits sulphur content. The dark green product resulting loses on oxidation the rest of its sulphur with the regeneration of flavanthrone.

Dimethoccy-dibenzanthrones. The condensation between dimethoxy dibenzanthrone zinc and sulphuric acid chloride yields a primary product which is almost insoluble in cold water. From this primary product a jade green colouring matter may be extracted by means of a warm solution of sodium carbonate of 4% strength. A product may also be obtained by extraction with large amounts of boiling water. Both products on salting out are easily soluble in cold water and appear to contain two atoms of sulphur.

In the examples given above, reference has been made specifically to benza'nthrone derivatives, indanthrone, flavanthrone, pyranthrone, anthraquinone-acridone, indigoid and indigo as types of vat dyestuifs.

The process of the invention is however general, and applicants know of no exception among the vat dyestuffs. In the examples given above the metal employed is zinc but m etals selected from the following may be used in place thereof, namely, magnesium, aluminium, cadmium, iron, cobalt, tin, antimony and copper.

We claim 1. Products which may be prepared by a process which consists in heating together a vat dyestufi, a liquid tertiary organic base, a metal of the group consisting of magnesium, aluminium, zinc, cadmium, iron, cobalt, tin, antimony and copper and cooling the product and mixing it with an alkyl sulphuric acid halide.

2. A process for the production of derivatives of vat dyestuffs which consists in heating together a vat dyestufl', a liquid tertiary organic base, a metal of the group consisting of magnesium, aluminium, zinc, cadmium, iron, cobalt, tin, antimony and copper, cool ing the product and mixing it with an alkyl sulphuric acid halide. a

3. A process for the production of derivatives of vat dyestuffs which consists in suspending the aforesaid dry vat dyestufi' in pyridine in the presence of a metal of the group consisting of magnesium, aluminium, zinc, cadmium, iron, cobalt, tin, antimony and copper, heating the mixture under reflux conditions, cooling the product, mixing it with alkyl sulphuric acid halide, adding a limited quantity of water and separating the residue from the liquor.

4. A process for the production of derivatives of vat dyestuffs which consists in suspending the aforesaid dry vat dyestufl' in pyridine in the presence of a metal of the group consisting of magnesium, aluminium,

zinc, cadmium, iron, cob-alt, tin, antimony and copper, heating the mixture under reflux conditions, cooling the product, mixing it with methyl sulphuric acid chloride, adding a limited quantity of water and separating the residue fromthe liquor.

5. A process asclaimed in claim 2, fo1-' lowed by treatment of the resulting solution with alkali, and isolation of the alkali salt thus formed. a

i 6. Products which may be prepared by a process which consists in heating together a vat dyestuff, a liquid tertiary organic base, a metal of the group consisting of ma esium, aluminium, zinc, cadmium, iron, co alt, tin, antimony and copper, cooling the product, mixing it with an alkyl sulphuric acid halide, extracting the primary product with alkali and isolating the alkali salt thus formed from the solution.

In testimony whereof we have signed our names to this specification. i

JAMES MORTON. JAMES IVOR MORGAN JONES. BIRKETT WYLAM. JOHN EDMUND GUY HARRIS. 

